KR101630679B1 - Method for polymerizing polyketone having low-melting point and polyketone having low-melting pointproduced using the same - Google Patents

Abstract

In the polymerization method of a low melting point polyketone in which polymerization is carried out in the presence of a polymerization catalyst according to an embodiment of the present invention, a hydrocarbon having 3 to 10 carbon atoms and at least one carbon monoxide containing at least one double bond in the molecule and carbon monoxide are introduced into a polymerization apparatus 1 < / RTI > polymerization reaction; And performing the second polymerization reaction by introducing ethylene after the first polymerization reaction proceeds 10% to 20%.

Description

TECHNICAL FIELD [0001] The present invention relates to a low-melting-point polyketone polymerization method and a low-melting-point polyketone using the same. BACKGROUND ART [0002]

The present technology relates to a polymerization method of a polymer and a polymer polymerized using the same.

A polyketone having a structure in which repeating units of a copolymer of carbon monoxide and an ethylenically unsaturated compound are substantially alternately linked has excellent mechanical and thermal properties and is excellent in abrasion resistance, chemical resistance and gas barrier property, to be. The high-molecular weight monomers of the fully alternating copolymer polyketone have higher mechanical and thermal properties, and are useful as engineering plastic materials having excellent economy. Particularly, it has high abrasion resistance and is used for parts such as gears of automobiles, and has high chemical resistance, so that it is used for a lining material of a chemical transportation pipe and has a high gas barrier property, so that it can be used for a light gasoline tank or the like. Further, when an ultrahigh molecular weight polyketone is used for a fiber, it is possible to stretch at a high magnification, and as a fiber having a high strength and a high elastic modulus oriented in a stretching direction, it can be used as a reinforcing material for belts, rubber hoses, tire cords, It is a material suitable for industrial material applications.

However, a polymerization method of polyketone using a palladium-based catalyst coordinated with various ligands has been proposed, but a polyketone having a sufficient yield and quality due to low catalytic activity has not been obtained.

US Patent Publication No. US 1985 / 782727A discloses a polyketone polymerization method in which a monomer such as ethylene or propylene containing carbon monoxide and a double bond is polymerized in the presence of a palladium-based catalyst. The polyketone polymerization is carried out by introducing propylene and then introducing carbon monoxide and ethylene at a predetermined ratio. The polyketone has a melting point determined by the content of propylene and an? -Olefin, and the higher the content of olefin in the polyketone, the lower the melting point. The? -Olefin having a long chain in the monomer is mainly used as? -Olefin because propylene is low in reactivity. Further, the catalyst system using 1,3-bis [non-2-methoxyphenyl) phosphino] propane as a ligand has a disadvantage that it is difficult to lower the melting point of the polyketone due to low activity.

U. S. Patent No. US1985 / 782727A

SUMMARY OF THE INVENTION The present invention has been made to overcome the problems of the prior art as described above, and it is an object of the present invention to provide a process for producing a palladium-based catalyst having high catalytic activity, which comprises reacting a hydrocarbon having at least one double bond and carbon monoxide A method of producing a low melting point polyketone by secondary polymerization by injecting highly reactive ethylene after polymerization and a low melting point polyketone using the same.

In the polymerization method of a low melting point polyketone in which polymerization is carried out in the presence of a polymerization catalyst according to an embodiment of the present invention, a hydrocarbon having 3 to 10 carbon atoms and at least one carbon monoxide containing at least one double bond in the molecule and carbon monoxide are introduced into a polymerization apparatus 1 < / RTI > polymerization reaction; And performing the second polymerization reaction by introducing ethylene after the first polymerization reaction proceeds 10% to 20%.

The polymerization catalyst may be a palladium-based catalyst coordinatively bonded to a ligand.

The ligand may be 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane represented by the following formula (1).

The hydrocarbon having 3 to 10 carbon atoms and containing at least one double bond in the molecule is preferably selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, Or a mixture thereof.

The first polymerization reaction may be carried out at a temperature of 82 ° C to 90 ° C, a pressure of 50 bar to 56 bar, and the second polymerization reaction may be carried out at a temperature of 82 ° C to 90 ° C, at a pressure of 50 bar to 56 bar.

The hydrocarbon and the carbon monoxide may be continuously or discontinuously introduced into the polymerization apparatus.

The ethylene can be continuously or discontinuously introduced into the polymerization apparatus, and can be introduced at the same rate as the carbon monoxide.

After completion of the second polymerization reaction, the temperature in the polymerization apparatus is lowered to 50 to 60 캜, and the obtained polymer is washed with alcohol, filtered and dried to obtain polyketone.

The polyketone may have a melting point of 160 ° C to 195 ° C.

The low melting point polyketone according to another embodiment of the present invention is produced by the above-mentioned production method.

According to the present invention, it is possible to obtain a polyketone having a high olefin content and a low melting point in a polymer chain in a high yield by using reactivity of the monomers charged and high activity catalyst and ligand. Further, according to the present invention, it is possible to enlarge the processing area such as the barrier film, the extrusion, and the bottle molding by using the polyketone having a low melting point.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart illustrating a process for producing a polyketone according to the present invention.
2 is a photograph of a device for measuring a BD (Bulk Density) value of a polyketone.
3 is a photograph of a device for measuring the intrinsic viscosity (IV) value of a polyketone.
4 is a graph plotting the content of monomers obtained by calculating the hydrocarbon content in the polyketone through NMR analysis.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be understood, however, that the embodiments described in the present specification and the constitutions shown in the drawings are only a preferred embodiment of the present invention, and that various equivalents and modifications can be made at the time of filing of the present application . DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, well-known functions or constructions are not described in detail to avoid obscuring the subject matter of the present invention. The following terms are defined in consideration of the functions of the present invention, and the meaning of each term should be interpreted based on the contents throughout this specification.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart illustrating a process for producing a polyketone according to the present invention.

1, in a polymerization method of a low melting point polyketone in which polymerization is carried out in the presence of a polymerization catalyst according to an embodiment of the present invention, a hydrocarbon having 3 to 10 carbon atoms and carbon monoxide containing at least one double bond in the molecule Introducing the mixture into a polymerization apparatus to perform a first polymerization reaction; And performing the second polymerization reaction by introducing ethylene after the first polymerization reaction proceeds 10% to 20%.

The polymerization apparatus has a stirrer capable of mixing a reaction solvent, a monomer, a polymer, etc. such as an impeller stirrer at a high speed and uniformly in a cylindrical vessel. The polymerization apparatus used in one embodiment of the present invention may be a polymerization apparatus for producing a polymer other than a polyketone. Further, it is preferable that a supply port capable of supplying gas and liquid into the vessel of the polymerization apparatus is provided. In one embodiment of the present invention, since the monomer of the polyketone is mainly supplied in a gaseous state, the pressure inside the vessel is greatly increased. Therefore, it is preferable to use the vessel designed to withstand the pressure of the gas.

Alcohol and water as a solvent are added to the polymerization apparatus, and the mixture is stirred while maintaining the speed from 300 rpm to 650 rpm from the beginning, and 3 to 10 carbon atoms including at least one double bond are introduced into the monomer through the monomer feed port. The hydrocarbon having 3 to 10 carbon atoms and containing at least one double bond in the molecule may be selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, And mixtures thereof. Depending on the kind of the hydrocarbon, the melting point of the polyketone produced after the polymerization varies. Therefore, depending on the use and properties of the obtained polyketone, the types of the hydrocarbons contained in the monomers may be varied to obtain polyketones of the required properties.

After the hydrocarbon is charged, the temperature is raised to the polymerization temperature. The polymerization temperature may be 82 ° C to 90 ° C, preferably 82 ° C to 88 ° C. When the temperature in the polymerization apparatus reaches the polymerization temperature, carbon monoxide is supplied from the monomer feed port. At this time, the pressure ratio between the hydrocarbon and the carbon monoxide may be 1: 2.3 to 1: 2.

When the carbon monoxide is supplied into the polymerization apparatus and the pressure in the polymerization apparatus reaches 30 bar to 35 bar, the first polymerization reaction (S110) is carried out by introducing a palladium-based catalyst coordinatively bonded to the ligand as a polymerization catalyst. The palladium-based catalyst may be palladium acetate (Pd (OAc) ₂ ). The ligand may be a ligand having an activity that can be used in polyketone polymerization. The ligand may be 3,3-bis- [bis- (2-methoxyphenyl) phosphonylmethyl] -1,5-dioxa-spiro [5,5] undecane represented by the following general formula (1). Trifluoroacetic acid (TFA) can be used as the acid used in this case, and trifluoroacetic acid plays a role of stabilizing bivalent palladium, that is, maintaining catalytic activity. The molar ratio of the catalyst may be palladium acetate: ligand: acid = 1: 1.05: 10 to 1: 1.2: 20.

[Chemical Formula 1]

When the reaction between the hydrocarbon and the carbon monoxide proceeded by 10% to 20%, that is, when the pressure inside the polymerization apparatus reached 25 bar to 30 bar, ethylene was introduced to perform the second polymerization reaction (S120). At this time, the supply amount of ethylene can be supplied at the same rate as the supply amount of the carbon monoxide. Stirring is continued until the polymerization is completed, and after the completion of the second polymerization reaction (S120), the inside of the polymerization apparatus is cooled to 50 to 60 캜. At this time, as the cooling method, cooling water and air may be used, but it is not limited thereto.

After the completion of the second polymerization reaction (S120), the obtained polymer is filtered using a filter, washed with alcohol, dried at 80 DEG C for 12 to 16 hours to obtain a polyketone (S130) . As the alcohol, methanol or ethanol may be used. At this time, the obtained polyketone has a melting point of 160 ° C to 195 ° C depending on the kind of the hydrocarbon.

The low melting point polyketone according to another embodiment of the present invention may be prepared by first introducing hydrocarbon and carbon monoxide having 3 to 10 carbon atoms containing at least one double bond into the molecule in the presence of a palladium- Polymerized by the reaction, and then ethylene is added thereto to carry out the second polymerization reaction. The low melting point polyketone is stable at high temperature and can be applied to a wider range than the grade applicable to existing products.

Since the method of polymerizing the low melting point polyketone has been described above, a description thereof will be omitted in order to avoid duplication.

Hereinafter, the present invention will be described more specifically by way of examples. However, the following examples are intended to aid understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

Example

[ Example  1 to Example  4]

2450 L and 40 L of methanol and water, respectively, were fed into the polymerization apparatus, and then 210 g, 260 g, 390 g and 520 g of propylene, 1-butene, 1-hexene or 1-octene were respectively added thereto with stirring as shown in Table 1 below. The polymerization temperature in the polymerization apparatus was raised to 90 DEG C, and carbon monoxide was introduced at a pressure in the range of 30 to 35 bar. Then, Pd (OAc) 2 / HKC-100 / TFA was added to conduct primary polymerization. When the polymerization was completed at 20%, ethylene was added in the same proportion as the carbon monoxide, and the secondary polymerization proceeded. After completion of the secondary polymerization, the temperature was lowered to 60 占 폚, the resulting polymer was washed with methanol, filtered and dried to obtain a polyketone containing propylene, 1-butene, 1-hexene or 1-octene .

Comparative Example

Methanol and water were fed into the reaction apparatus, and propylene was added thereto with stirring. The polymerization temperature was raised to 90 DEG C, and carbon monoxide and ethylene were fed at a ratio of 1: 1 to a polymerization pressure of 56 bar. Then, Pd (II) -bidentate phosphine Ligand-Acid was added as a catalyst to proceed polymerization. After the polymerization, the temperature was lowered to 60 DEG C, and the resulting polymer was washed with methanol, filtered and dried to obtain a polyketone. At this time, the melting point of the obtained polyketone was 234 占 폚.

evaluation

The properties of each of the polyketones obtained in Examples 1 to 4 were measured and shown in Table 1.

division hydrocarbon
(6 mol %) activation
( kg / g. Pd / h) BD
(g / ml ) IV
( dL / g) Melting point (캜) Monomer
content( mol %) Example 1 Propylene 4.1 0.12 0.52 192 11.6 Example 2 1-Butene 3.6 0.13 0.46 193 3.07 Example 3 1-Hexene 2.6 0.25 0.41 173 4.99 Example 4 1-Octene 1.7 0.23 0.43 163 6.99 Comparative Example 1 Propylene 14.9 0.07 1.30 234 4.48

1. Active

The activity in the above Table 1 was obtained by calculating the production amount per hour relative to the amount of palladium input.

2. BD ( Bulk Density )

The BD in Table 1 represents the weight within a certain volume, and the improvement of BD is a factor affecting the production amount and the post-process improvement. The polyketone powder was put into the equipment shown in FIG. 2, and the weight of the powder was measured by dropping it in a container of 100 ml volume to obtain a BD value.

3. IV  ( Intrinsic viscosity )

IV in Table 1 is for measuring the flow of the solution by dissolving the powder in a predetermined concentration, and relates to the size and molecular weight of the molecule. The polyketone powder was dissolved in the HFIP solution at a predetermined concentration in the equipment shown in Fig. The Uve Rod tube was placed in the IV analysis equipment and the IV time was measured by measuring the drop time at 25 degree.

4. Melting point

The melting point of Table 1 indicates the temperature at which the characteristic changes from a rubber-like property to a liquid-like property, and the lower the melting point, the more various grades can be applied. When measuring the melting point, the temperature was elevated twice to measure the melting point. After the temperature was raised from room temperature to 250 ° C (first temperature increase), the temperature was again cooled to room temperature. When the temperature reached room temperature, the temperature was again raised to 250 ° C (second temperature elevation) to obtain a melting point. At this time, the primary heating is aimed at thermal history analysis and the result of the secondary heating is the result of the melting point of the polyketone.

5. Monomer  content( mol %)

NMR analysis of the content of hydrocarbons in polyketones. The structure of the polyketone can be analyzed by 400 MHz 1H NMR analysis. There is a polymer having various forms in the polyketone molecule. When a monomer such as propylene, 1-butene, 1-hexene or 1-octene is charged, a peak like 'd' in the graph shown in FIG. 4 exists . The results can be obtained by calculating the monomer content through the proton values.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. The scope of the present invention should be interpreted based on the scope of the following claims and all technical ideas within the scope of equivalents thereof are to be construed as being included in the scope of the present invention. It is to be understood that the invention is not limited thereto.

Claims (12)

A method for polymerizing a low melting point polyketone which is polymerized in the presence of a palladium-based polymerization catalyst coordinatively bonded to a ligand,
Performing a first polymerization reaction by introducing a hydrocarbon having 6 to 10 carbon atoms containing at least one double bond in the molecule and carbon monoxide into a polymerization apparatus; And
And performing a second polymerization reaction by introducing ethylene after the first polymerization reaction proceeds 10% to 20%
The ligand is a 3,3-bis- [bis- (2-methoxyphenyl) phosphonylmethyl] -1,5-dioxa-spiro [5,5] undecane represented by the following formula Lt; / RTI >
[Chemical Formula 1]

The method according to claim 1,
The hydrocarbon having 6 to 10 carbon atoms, which contains at least one double bond in the molecule,
Wherein the polyketone is at least one member selected from the group consisting of 1-hexene, 1-octene, and mixtures thereof.
The method according to claim 1,
Wherein the first polymerization reaction is carried out at a temperature of 82 DEG C to 90 DEG C, at a pressure of 30 bar to 35 bar.
The method according to claim 1,
Wherein the second polymerization reaction is carried out at a temperature of from 82 DEG C to 90 DEG C, at a pressure of from 50 bar to 56 bar.
The method according to claim 1,
The hydrocarbons and the carbon monoxide,
Continuously or discontinuously into the polymerization apparatus.
The method according to claim 1,
The ethylene,
Continuously or discontinuously into the polymerization apparatus.
The method according to claim 1,
The ethylene,
Wherein the carbon monoxide is introduced at the same rate as the carbon monoxide.
The method according to claim 1,
After completion of the second polymerization reaction, lowering the temperature in the polymerization apparatus to 50 ° C to 60 ° C, washing the resulting polymer with alcohol, filtering and drying to obtain a polyketone Way.
9. The method of claim 8,
Wherein the polyketone has a melting point of 160 캜 to 195 캜.
A polyketone prepared by the process of any one of claims 1 to 9.

delete delete

Images